Certificate of .correction

ABSTRACT

PREPARING PEROXYETHERS (PEROXYACETALS AND PEROXYKETALS) BY REACTING ALKYLIDENE DIPEROXIDE WITH DIVALENT ALCOHOL, DESIRABLY IN THE PRESENCE OF AN ACID CATALYST.

y No Drawing. Original No. 3,468,962, dated Sept. 23, 1969, Ser. No. 550,643, May 17, 1966. Application for reissue Sept. 14, 1971, Ser. No. 180,484

Claims priority, ap ilicztifnsgtaly, May 21, 1965,

1.11. CI. con 41/00, 43/30, 73/00 US. or. 260-610 n 18 Claims Matter enclosed in heavy brackets II II appears in the orignal patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

ABSTRACT OF THE DISCLOSURE Preparing peroxyethers [peroxyacetals and peroxyketals] by reacting alkylidene diperoxide with divalent alcohol, desirably in the presence of an acid catalyst.

The present invention relates to a new process for preparing peroxyacetals and peroxyketals. In particular, it is concerned with the transemiacetalation [transsemiacetalation] of alkylidenediperoxides, i.e., the substitution [substitution] of an alkoxy group for an alkyl peroxy group in an alkylidenediperoxide by exchange with a monoor divalent alcohol, either in the presence or absence of acid catalysts.

In one embodiment, the invention relates to a method for the transemiacetalation [transsemiacetalation] of an alkylidenediperoxide prepared in situ, with a monoor divalent alcohol, in the presence of an acid catalyst.

Peroxyacetals or peroxyketals, which may also be called peroxyethers, are characterized by the presence of an alkoxy group (OR) and of a peroxy group (-OOR') linked to the same ternary or quaternary carbon atom. Previously proposed methods for the preparation thereof include the addition of an organic hydroperoxide to an alpha-unsaturated ether in the presence of acid catalysts in a homogeneous or heterogeneous system. According to a particular method disclosed in our copending U.S. patent application Ser. No. 505,761, filed on Oct. 29, 1965, solid catalysts are employed, such as e.g., cationic resins, active carbon, acid mineral salts and the like.

Peroxyketals can also be prepared by heating an acetal with an alkylhydroperoxide at 90 C. (see Rieche et al., Chem. Ber. 94, 2457 (1961)).

In both cases, these methods require availability of raw materials, such as alpha-unsaturated ethers or acetals, which can be prepared only with difiiculty and cannot be conveniently produced in large-scale commercial quantities.

In addition, the preparation of alkylideneperoxides by reaction between a carbonyl compound (aldehyde or ketone) and an organic hydroperoxide has been previously proposed. This reaction takes place in the presence of acid catalysts and uses readily available raw materials. In particular, in copending application Ser. No. 434,620, filed Feb. 23, 1965, solid compounds of acidic nature, such as cationic exchange resins and active earths, have been proposed for use as catalysts in a process which is suitable as a continuous process with a fixed-bed catalyst.

It has now been found that peroxyacetals and peroxyketals can be prepared by a reaction involving simply heating an alkylideneperoxide with a monoor divalent alcohol, preferably in the presence of acid catalysts.

The present invention therefore provides a process for i United States Patent "ice the preparation of peroxyacetals and peroxyketals having the general formulae:

R: Rr-O-D--O-Rt and R: H H Rt wherein R is a hydrogen atom or an alkyl, cycloalkyl or aralkyl radical containing up to 10 carbon atoms; R is an alkyl or aralkyl radical containing up to 10 carbon atoms; R: and R are hydrogen atoms, alkyl or cycloalkyl radicals containing up to 10 carbon atoms, which radicals may be halogen-substituted, or one of the two radicals R, or R, can be also or R, and R may, taken together and in conjunction with the central carbon atom (C) to which they are bonded [from] form a [cycloaliphatric] cycloaliphatic ring; R, is a primary or secondary alkyl, aralkyl or cycloalkyl radical containing up to 10 carbon atoms; and R is an alkylene, cycloalkylene, or arylene radical containing up to 10 carbon atoms, which radical may be alkylor halogen-substituted, or R is -(R O),,R wherein R, and R are lower alkylene and n is an integer from 1 to 9, which process comprises reacting an alkylidenediperoxide having the formula:

wherein R R, and R are as defined above, with a monovalent alcohol, R 0H, or with a divalent alcohol having the formula:

wherein R,, R and R are as defined above, the reaction being continued until 1 mo] of hydroperoxide,

Rr-O-OH is liberated per mol of starting alkylidenediperoxide.

During this reaction an exchange occurs first between only one peroxy group (O0R of the alkylidenediperoxide and an alkoxy group (e.g., -0R,) with the formation, as a lay-product, of hydroperoxide (R 00H).

The reaction leads to an equilibrium. Thus, in order to obtain the desired product, it is convenient to operate in the presence of an excess of reactants, preferably of the alcohol and/or to remove the formed hydroperoxide continuously, e.g., by distillation. The removal of the formed hydroperoxide can be effected by distillation under vacuum or with the use of an azeotroping agent.

Removal of the formed hydroperoxide is the preferred expedient when the boiling point of the formed hydroperoxide or of the azeotrope is lower than that of the reactants and in particular of the alcohol. When this is not the case, the shifting of the reaction toward the desired product will be made easier by using an excess of alcohol.

In order to avoid further progression of the reaction, which would result in the exchange of an alkoxy group with the second peroxy group of the alkylidenediperoxide, with formation of the corresponding ketal or acetal, it is convenient to stop the reaction by cooling when the stoichiometric amount of hydroperoxide, corresponding to 1 mol per mol of starting alkylidenediperoxide, is formed. It has been ascertained, furthermore, that the rate of the second stage of transaeetalation is much lower than that of the first stage and furthermore, that he process is reversible in he presence of free hydroperoxide.

The transacetalation reaction is carried out at a temperature ranging from C. to 100 C., preferably from 0 C. to 90 (3., either in the presence or absence of acid catalysts, the alkylidenediperoxide and the monoor divalent alcohol being present in molar ratios ranging from a considerable excess of either one of the two reactants (varying from about 4:1 to 1:5 mols to the stoichiometric quantity (1:1 and 2:1 mols, respectively, depending on whether a monovalent or divalent alcohol is used). An excess of alcohol is preferably employed.

The alkylidenediperoxides which may be reacted with monoor divalent alcohols in the process of the present invention include, e.g.z

l,l-di-tertbutylperoxyethane l 1-di-tert.butylperoxyp ropane 2,2-di-tert.butylperoxypropane 2,2-di-tert.butylperoxybutane Alpha,alpha-di-tert.butylperoxytoluene Alpha,alpha,alpha',alpha'-tetra-tert.butylperoxyxylenes 1,l-di-tert.butylperoxy-cyclopentane 1 l -ditert.butylperoxy-3 ,5 ,S-trime thyl-cyclohexane Beta,beta'-di-tert.butylperoxy-methylbutyrate Beta,beta-di-tert.butylperoxy-ethylbutyrate Gamma,gamma-di-tert.bntylperoxymethylvalerate Gamma,gamma-di-tert.butylperoxyethylvalerate In general, there may be employed the alkylidene-diperoxides derived from the reaction between an aliphatic, cycloaliphatic, aromatic, carbonyl or polycarbonyl compound such as, e.g., acetone, acetylacetone, diacetonealcohol, cyclohexanone, cyclohexanedione, benzoylacetone, formaldehyde, acetaldehyde, benzaldehyde, etc., and an organic hydroperoxide, in particular tert.butylhydroperoxide. Such reaction may be conducted in the presence of acid catalysts (e.g., by the method disclosed in US. Pat. 2,455,569) or in the presence of heterogeneous acid catalysts (as in the method disclosed in application Ser. No. 434,620, filed on Feb. 23, 1965).

In accordance with an alternative embodiment of the present invention, the alkylidenediperoxide can be formed in situ. In this case, the process of the invention starts by first reacting carbonyl compounds, hydroperoxides and alcohols, in the presence of acid catalysts, to form the alkylidenediperoxides, this being followed, in situ, by the transemiacetalation [transsemiacetalation] reaction to form the peroxyacetals or peroxyketals, without separating of the intermediate product.

The alcohols which may be used in the present invention are primary or secondary aliphatic alcohols, cycloaliphatic alcohols, aliphatic glycols, primary or secondary alkylaromatic alcohols etc. These include, e.g., methanol, ethanol, higher aliphatic alcohols containing up to 18 carbon atoms, cyclopentanol, terpenols, benzyl alcohol, butanediol-l,3; butanediol-l,4; pentanediol-1,3; pentane diol-1,4 [1.4]; diethylene glycol, polyethylene glycol, mxylylene glycol, p-xylylene glycol and the monoalkyl ether of ethylene glycol.

The acid catalysts which may be employed to accelerate the rate of the transemiacetalation [transsemiacetalation] reaction can be either soluble or insoluble in the reaction medium. The soluble catalysts include for example mineral acids, such as HCl, HBr, H PO HF, BF, and H and organic sulfonic acids. Among the insoluble catalysts that can be used according to this invention can be mentioned silicic acids (also silica gel), organic sulfonic acids, heteropolyacids, active acidic earths, ion exchange cationic resins (H form), acidic alumina, active carbons, Friedel-Crafts type catalysts and acid carbon blacks.

The amounts of homogeneous acid catalyst which are generally used to accelerate the transemiacetalarion [transsemiacetalation] reaction are preferably between about 0.01 and 50.0 parts by weight per parts of reaction mixture.

The process of the present invention can be conveniently carried out continuously by passing the reactants into a column through a fixed bed of heterogeneous acid catalyst.

Carrying out the process of the present invention in the presence of solvent can prove to be advantageous, especially when the alkylidenediperoxide and the alcohol are poorly soluble in each other. As solvents, inert type solvents are generally used, e.g., dioxane, diethyl ether, petroleum ether, pentane, hexane, heptane, cyclohexane, benzene, toluene, xylene, decane, Tetralin, Decalin, etc.

The peroxyacetals and peroxyketals prepared according to the process of the present invention are particularly useful as free radical polymerization initiators curing agents for elastomers, cross-linking agents for plastomers, agents for improving the centane number of gasolines, etc.

The following examples are intended to further illustrate the present invention without restricting its scope.

EXAMPLE I.PREPARATION OF Z-METHOXY-Z- TERTBUTYLPEROXYPROPANE 55 g. of 2,2-di-tert.butylperoxypropane, 16 g. of methanol and 1 g. of cationic exchange resin, Kastel (3-300, were introduced into a 250 cc. flask. The mixture was kept under agitation and heated under reflux on a water bath. At regular intervals two samples of 0.1 cc. were taken in order to determine free hydroperoxide iodometrially;

Active oxygen present in peroxidic form and active oxygen present in hydroperoxidic form can be separately iodometrically analyzed. (See, e.g., Dickey et al., J. Amer. Chem. Soc. 71, 1432 (1949).)

The total active oxygen present in the reaction mixture was determined by treating the 0.1 cc. sample with 25 cc. of glacial acetic acid and 2 g. of potassium iodide, and boiling for 25 minutes in a flask provided with a reflux condenser. After washing the condenser with 50 cc. of water, titration was carried out at room temperature with a N/lO solution of sodium thiosulfate. Hydroperoxidic active oxygen was determined by treating the second 0.1 cc. sample with 50 cc. of isopropanol, 2 cc. of glacial acetic acid and 2 cc. of a saturated KI solution, and boiling for 2 minutes under reflux. After washing the condenser with 50 cc. of water, titration was carried out at room temperature with a N/lO solution of sodium thiosulfate.

Peroxidic active oxygen was calculated by difierence between total active oxygen and hydroperoxidic active oxygen thus determined.

The values of the ratio,

hydroperoxidic active oxygen corresponding to the yield of formed monoperoxyketal are reported in the following table as a function of time:

TABLE 1 Time (minutes) Percent monoperoxyketal hydroperoxidit active oxygen X peroxidic active oxygen After about 3 hours of reaction, the formed peroxide was separated from the resin by filtration, and then washed free of excess methanol by washings with 15% aqueous solutions of NaOH.

38 g. were obtained of a substance which was then distilled under vacuum. The fraction boiling at 33-34 C./ 10 mm. Hg was collected. This fraction weighed 31 g. and was identified as 2-methoxy-2-tert.butylperoxypropane. Its characteristics were:

Found Calculated Deuslt no 1. 4003 Molecu ar weight 168 162 Active oxygen (percent 9. 5 9. 87 Percent carbon 63. ii 53. 3 Percent hydrogen 9. 3 9. 47

The yield with respect to starting 2,2-di-tert.butylperoxide was 74%.

EXAMPLE 2 55 g. of 2,2-di-tert.butylperoxy-propane, 50 cc. of dioxane, 20 cc. of methanol and 2 g. of sulfonated resin of the type Kastel G-300 (in acid form) were introduced into a flask provided with a stirrer and a reflux condenser maintained [maintaind] at 65 C. in a water bath.

The course of the reaction was followed by determining the ratio hydroper'oxidic active oxygen peroxidic active oxygen as described in Example 1.

The values of this ratio as a function of time are reported in the following table:

TABLE 2 Time (minutes): Percent monoperoxyketal formed 0 After 3 hours, the reaction was stopped and dioxane was distilled ofi at 50-35 C./70 mm. Hg. Then Z-methoxy-2-tert.butylperoxypropane was isolated as described in Example 1. 28 g. of the peroxide were obtained, corresponding to a yield of 66.5%.

EXAMPLE 3 55 g. of 2,2-di-tert.butylperoxypropane, 20 cc. of methanol and 1 g. of W.M. Valdol earth (acidity, 65 meq./100 g.) having the following composition by weight:

Percent SiO, 64.74 A1 0 1 1.35 MgO 0.74 CaO 2.82 Fe303 2.58

Percent TiO, Traces S0 n 0.11 H O 5.23

were reacted in a flask provided with a stirrer and a reflux condenser, kept at a temperature of 65 C.

As in Example 1, the course of the reaction was followed by iodometric determination of active oxygen.

The values of the ratio:

hydroperoxidic active oxygen peroxidic active oxygen are reported in the following table as a function of time:

TABLE 3 Time (minutes): Percent monoperoxyketal formed 0 30 3.6 60 9.0 90 I 13.1 18.6 j 22.8 27.0 210 n, 29.0 240 30.0

After 3 hours, the reaction was stopped and Z-methoxy- 2-tcrt.butylperoxypropane was separated from the catalyst and isolated as described in Example 1.

8.2 g. of peroxide were obtained, corresponding to a yield of 20.2%.

EXAMPLE 4 55 g. of 2,2-di-tert.butylperoxypropane [butyleperoxypropane], 20 cc. of methanol and 2 g. of potassium bisulfate (Carlo Erba, Milan, pure product for analysis) were reacted in a flask provided with a stirrer and a reflux condenser, kept at 65 C.

The following table shows the percentage values of monoperoxyketal formed, as a function of time deter The reaction was then stopped and 2-methoxy-2-tert.- butylperoxypropane was isolated as described in Exampie 1.

8.5 g. of peroxide were obtained, corresponding to a yield of 21%.

EXAMPLE 5 55 g. of 2,2-di-tert.butylperoxypropane, 20 cc. of methanol and 2 g. of anhydrous colloidal silicic acid (hydrated silica, Hi-Sil 233, Columbia-Southern Chemical Corporation) having the following composition (by weight) and properties:

SiO, p cent..- 27 [87] CaO 0.5 A1 0,, 0.6 H 0 [(approx.)] do..-.. 10.0 NaCl (approx.) do 1.0 pH 7 Surface area m./g 150 were introduced into a flask provided with a stirrer and a reflux condenser kept at a temperature of 65 C.

The course of the reaction was followed by the iodo metric analysis described in Example 1. The percentage 7 values of the monoperoxyketal formed are reported in the following table as a function of time:

TABLE 5 Percent monoperoxyketal Time (minutes): formed The reaction was then stopped and Z-methoxy-Z-tert. butylperoxypropane was isolated as described in Example 1.

7.2 g. of peroxide were obtained, corresponding to a yield of 17.8%.

EXAMPLE 6 55 g. of 2,2-di-tert.butylperoxypropane, 20 cc. of methanol and 2.5 g. of carbon black Kosmobil 77 (United Carbon Company) having the following characteristics:

Surface area m./g 116 Diameter of the particles mp..... 27 Volatile substances percent 5.7 pH 4.3

were introduced into a flask provided with a stirrer and a reflux condenser, kept at a temperature of 65 C.

The course of the reaction was followed by iodometric titration of the active oxygen as described in Example 1. The results are reported in the following table:

The reaction was then stopped and Z-methoxy-Z-tert. butylperoxypropane was isolated as described in Example 1. 9.5 g. of peroxide were obtained, corresponding to a yield of 23.5%.

EXAMPLE 7 220 g. of 2,2-tert.butylperoxypropane and 100 cc. of ethanol were introduced into a flask provided with stirrer, separatory funnel and thermometer. The solution was externally cooled with a cryoscopic mixture at 0 C. and cc. of concentrated HCl were slowly added, the temperature not being allowed to exceed 0 C.

The mixture was maintained under agitation at 0 C. for 2 hours and then poured into water and the upper layer separated.

The reaction product was washed with water and then with a 10% aqueous solution of NaOH to remove the formed hydroperoxide and was [as] thereafter dried over anhydrous Na sOs 2-ethoxy-2-tert.butylperoxypropane was isolated by fractional distillation under vacuum, the fraction boiling at 47-48" C. mm. Hg being collected.

105 g. of product corresponding to a 60% yield were obtained. It had the following characteristics:

8 EXAMPLE 8 165 g. of 2,2-di-tert.butylperoxypropanc, 200 g. of 2- ethylhexyl alcohol and 2 g. of p-toluenesulfonic acid were introduced into a flask which was maintained at 70 C. under a vacuum of 45 mm. Hg for 2 hours.

The residue was then washed with a 10% aqueous solution of NaOH and dried. The unreacted 2-ethylhexanol and the unreacted 2,2-di-tert.butylperoxypropane were distilled oil under vacuum keeping the bath at 60 C. and the vacuum at 1 mm. Hg. Then the residue was passed through a chromatographic column filled with allumina (for chromatography) and eluted with petroleum et er.

After evaporation of the solvent, 146 g. of 2-(2-ethylhexoxy [hexoyl])-2-tert.butylperoxypropane, corresponding to a yield of 75%, were obtained. It had the following characteristics:

Found Calculated d 0 8280 no! 1. 4240 Percent active oxygen 6. 25 0. l0 Gryoscopic mulecular [moccular welghtl.-. 27B 260 EXAMPLE 9 Found Calculated 0. 8572 up 1.4238 Percent active or en 6. 2 0. 45 Cryoscopic molecu ar weight 248 260 EXAMPLE 10 55 g. of 2,2-di-tert.butylperoxypropane, 120 g. of benzyl alcohol and 2 g. of cationic resin Kastel (3-300 were introduced into a flask provided with a reflux condenser and a stirrer. The mixture was kept under agitation at C. for 1 hour and then filtered to remove the resin.

The filtrate was washed with water, then with a 10% aqueous solution of NaOH to remove the formed hydroperoxide and the residue was then dried over anhydrous Na SO The product thus obtained was distilled under a vacuum which was allowed to increase to 0.5 mm. Hg, while the bath was kept at 60 C. so as to distill 011' all of the 2,Z-di-tert.butylperoxypropane and as much as possible of the unreacted benzyl alcohol.

The thus obtained residue was then chromatographically analyzed in a column over A1 0, and eluted with petroleum ether.

The residue, after solvent evaporation, corresponds to 2-benzyloxy-2-tert.butylperoxypmpane, having the following characteristics:

Found Calculated no" 1. 4041 Percent active or en 6. 0 7. 2 Cryoscoptc molecu ar weight 215 222 EXAMPLE 11 A mixture consisting of 55 g. of 2,2-di-tert.butylperoxypropane and cc. of methanol was introduced into a flask provided with a reflux condenser. Samples were taken at the times given below in order ot determine the hydroperoxide formed, as described in Example 1, while keeping the reaction mixture at the boiling point in a water bath.

TABLE 7 Percent monoperoxy- Time (minutes): ketal formed 0 30 6.3 60 10.2 90 15.2 120 28.0 150 39.8 180 52.3 210 72.7 240 87.0

29.5 of 2-methoxy-2-tert.butylperoxypropane were obtained, corresponding to a yield of 73%.

EXAMPLE 12 55 g. of 2,2-di-tert.butylperoxypropane, 55 g. of diethylene glycol, 150 cc. of dioxane and 3 g. of ion-exchange resin Kastel 0-300 were introduced into a flask provided with a stirrer and a reflux condenser. The mixture was kept under agitation at 80 C. for 2.5 hours and then filtered to remove the resin.

The filtrate was subjected to vacuum distillation at 70 mm. Hg to distill off the dioxane and the residue was then poured in water. The upper organic layer was separated and washed three times with a 10% aqueous solution of NaOH.

After drying over Na SO the resulting product was distilled under a vacuum which was allowed to increase to 0.5 mm. Hg, while keeping the batch at 65 C. The residue was then passed through the chromatographic column filled with A1 0 and eluted with petroleum et er.

The product obtained after evaporation of the solvent, 3,0 di[ (2 ternburylperoxy)-isopropoxy]-diethyl [di[(2- tert.butylperoxy)isopropoxy]diethyljlether,

EXAMPLE 13 58 g. of acetone, 45 g. of tert.butylhydroperoxide and 64 g. of methanol were introduced into a flask provided with a stirrer, thermometer and separatory funnel, and the mixture was externally cooled with ice to 0 C. 10 cc. of concentrated HCl were added dropwise, the temperature of the solution not being allowed to exceed 5 C.

After 30 minutes reaction, the mixture was poured into water and the upper organic layer was separated and washed first with water and then three times with NaOH and dried over Na SO A crude product weighing 32 g. was obtained and subiected to fractional distillation under vacuum through a Widmcr column. The following fractions were collected:

EXAMPLE 14 A column (25 mm. internal diameter, 2000 mm. length) provided with an external heating jacket was filled with a 10 sulfonic ion-exchange resin of the Kastel 0-300 type and kept at a constant temperature of 60 C. by circulating warm water in the external heating jacket.

A mixture of 2,2-di-tert.butylperoxypropane and methanol, in a molar ratio of 1:2, was passed downward through this column from top to bottom at a flow rate of 12-15 ccJrninute. The liquid coming out from the column was poured into water and 2-methoxy-2-tert.butylperoxypropane was isolated from the separated upper organic layer as described in Example 1.

EXAMPLE 15 39 g. of 1,l-di-tert.butylperoxycyclohexane and 50 cc. of ethanol were introduced into a flask. 3 g. of cationic ion-exchange resin of the Kastel C-300 type were added and the mass kept at reflux over a bath maintained at a constant temperature of C. After two and a half hours, the reaction mixture was filtered to remove the resin and the filtrate was washed three times with water and then thrice with a 10% aqueous solution of NaOI-I.

The mixture was dried over Na SO and distilled under vacuum. 1 methoxy 1-tert.butylperoxycyclohexane was collected at 48-50 C./0.5 mm. Hg.

17.6 g. of peroxide were obtained, which corresponds to a yield of 58%.

The obtained product had the .following characteristics:

Found Calculated no" l. 4408 Active oxygen 7. 5 7. 9

R: lh-O-O-(J-O-Rt I wherein R is an alkyl or aralkyl radical containing up to 10 carbon atoms; R, and R are hydrogen atoms, alkyl or cycloalkyl radicals containing up to 10 carbon atoms, which radicals may be halogen-substituted, or one of the two radicals R or R; can be also --R.c-R:

DDR1

wherein R is an alkylene, cycloalkyiene, or arylene radical containing up to 10 carbon atoms, which radical may be alkyl or halogen substituted, or R is (R5O) -R7 wherein R and R are lower alkylene and n is an integer from I to 9, or R and R may, taken together and in conjunction with the central carbon atom (C) to which they are bonded to form a cycloaliphatic ring; R is a primary or secondary alkyl, aralkyl or cycloalkyl radical containing up to 10 carbon atoms, said process comprising reacting, at a reaction temperature in the range of from about -15 C. to C., in the presence of from about 0 to 50 parts by weight of acid catalyst per 100 parts of the reaction mixture, (1) an alkylidenediperoxide having the formula:

s Br-O-O--O-O-Jh I (III) wherein R R, and R are as defined above, with (2) a monovalent alcohol, R 0H, wherein R is as defined 1 1 above, the molar ratio of said alkylidenediperoxide to said alcohol being in the range of from about 4:1 to 1:5, and continuing the reaction nntil up to 1 mol of hydroperoxide, R.;-OOH, is liberated per mol of said starting alkylidenediperoxide.

2. The process of claim 1 wherein the reaction is carried out at a temperature in the range of from about C. to 90 C.

3. The process of claim 1 wherein the reaction is carried out in the presence of an acid catalyst.

4. The process of claim 1 wherein the reaction is carried out in the absence of an acid catalyst.

5. The process of claim 1 wherein an excess of alcohol is used.

6. The process of claim 1 wherein stiochiometric amounts of the alkylidenediperoxide and the alcohol are used.

7. The process of claim 1 wherein the alkylidenediperoxide is prepared in situ.

8. The process of claim 3 wherein the acid catalyst is selected from the group consisting of mineral acids, silicic acids, sulfonic acids, heteropolyacids, acid earths, cationic exchange resins in acid form, acid alumina, active carbons, Friedel-Crafts type catalysts and acid carbon blacks.

9. The process of claim 1 wherein the alcohol is selected from the group consisting of primary and secondary aliphatic alcohols, eycloaliphatic alcohols, aliphatic glycols, and primary and secondary alkyl aromatic alcohols.

10. A process for preparing peroxyethers of the general formula:

s a (11) wherein R is a hydrogen atom or an alkyl, cycloalkyl or aralkyl radical containing up to 10 carbon atoms; R, is an alkyl or an aralkyl radical containing up to 10 carbon atoms; R, and R are hydrogen atoms, alkyl or cycloalkyl radicals [radical] containing up to 10 carbon atoms, which radicals may be halogen-substituted or one of the two radicals R or R, can be also or R; and R may, taken together and in conjunction with the central carbon atoms (C) to which they are bonded form a eycloaliphatic ring; and R is an alkylene, cycloalkylene, or arylene radical containing up to carbon atoms, which radical may be alkyl or halogen substituted, or R is --(R 0),,R wherein R, and R are lower alkylene and n is an integer from 1 to 9, said process comprising reacting at a reaction temperature in the range of from about --l5 to +100 C. in the presence of from about 0 to 50 parts by weight of acid catalyst per 100 parts of the reaction mixture, an alkylidenediperoxide having the formula:

wherein R R and R are as defined above with a divalent alcohol having the formula wherein R and R are as defined above, the molar ratio of said alkylidenediperoxide to said alcohol being in the range of from about 4:1 to 1:5, and continuing the reaction [up] until up to 1 mol of hydroperoxide, R 00H, [R-0OH,] is liberated per mole of said starting a1kylidenediperoxide.

11. The process of claim 10 wherein the reaction is carried out at a temperature in the range of from about 0 C. to C.

12. The process of claim 10 wherein the reaction is carried out in the presence of on acid catalyst.

13. The process of claim 10 wherein the reaction is carried out in the absence of an acid catalyst.

14. The process of claim 10 wherein an excess of alcohol is used.

15. The process of claim 10 wherein stiochiometric amaolu'nts of the alkylidenediperoxide and the alcohol are as 16. The process of claim 10 wherein the alkylidenediperoxide is prepared in situ.

17. The process 0 claim 12 wherein the acid catalyst is selected from the group consisting of mineral acids, silicic acids, sulfonic acids, heteropoly acids, acid earths, cationic exchange resins in acid form, acid alumina, active carbons, Friedel-Crafts type catalysts and acid carbon blacks.

18. The process of claim 10 wherein the alcohol is selected from the group consisting of primary and secondary aliphatic alcohols, cycloaliphatic alcohols, aliphatic glycols, and primary and secondary alkyl aromatic alcohols.

No references cited.

BERNARD HELFIN, Primary Examiner W. B. LONE, Assistant Examiner T3253? U lVITED STATES PATENT OFFICE CERTIFICATE OF :CORRECTION Patent No. Re.27, 843 Dated December 18, 1973 Inventor(s) Giuliano Ballini et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

gplumn 1, line 20, ABSTRACT: "reacting alkylidene" should read reacting an alkylidene Column 1, line 20,ABSTRACT:

"with divalent" should read with a divalent Column 1, line 28: "[substitution] should read [substition] Column 1, line 28: "alkyl peroxy" should read alkyl peroxy Column 1, line 31: "of acid" should read of an acid Column 1, line 31: "catalysts" should read catalyst Column l,- line 44: "acid" should read an acid Column 1, line 44: "catalysts" should read catalyst Column 1, line 61: "acid" should read an acid Column 1, line 61: "catalysts" should read catalyst Column 1, line 63: "of acidic" should read of an acidic Column 1, line 71: "of acid" should read of an acid Column 1, line 71: "catalysts" should read catalyst Column 3, line 4: "particular" should read particular, Column 3, line 17: "he" should read the Column 3, line 18: "he" should read the Column 3, line 22: "of acid" should read of an acid Column 3, line 22: "catalysts" should read catalyst Column 3, line 53: "of acid" should read of an acid Column 3, line 53: "catalysts" should read catalyst Column 3, line 54: "of heterogeneous" should read of a heterogeneous Column 3, line 55: "catalysts" should read catalyst Column 3, lines 64-65: "separating" should read separation Column 4, line 31: "initiators" should read initiators,

Column 4, lines 49-50: "to determine the free hydroperoxide iodometrically. should read to iodometrically determine the amount of free hydroperoxide.

PC3-1050 UNITED STATES PATENT OFFICE PAGE 2 CERTIFICATE OF CORRECTION Patent No. Re. 27,843 Dated December 18, 1973 Inventor(s) Giuliano Bellini et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 4, line 69: "by" should read" as the Column 5, line 6: "hydroperoxidit" should read hydroperoxidic Column 8, line 72: "0t" should read to Column 9, line 16: "29.5 g. should read 29.5 g. of Column 10, line 42: "R" should read R Column 11, line 48: "atoms" should read atom Signed and sealed this 10th day of September 197 (SEAL) Attest;

MCCOY M. GIBSON, JR. C. MARSHALL DANN Attesting Officer Commissioner of Patents 

